JP5114117B2 - Cellulose-containing biodegradable resin composition and foam thereof - Google Patents

Description

  The present invention relates to a cellulose-containing biodegradable resin composition using a root vegetable squeezed rice cake and a biodegradable foam using the same.

  Conventionally, so-called plastic materials, which are synthetic resins, have been widely used from the viewpoint of convenience, and attempts have been made to improve their functions and physical properties. As a result, many plastic materials are very stable and do not readily decompose when discarded, and many generate harmful gases when incinerated during disposal. From the viewpoint of protection, the focus of research and development has shifted to improving recyclability and biodegradability rather than pursuing convenience.

  As biodegradable plastic materials, materials based on natural materials such as starch, cellulose, and cellulose acetate have been developed together with synthetic resins such as aliphatic polyester, polycaprolactone, and polylactic acid. Among these, cellulose represented by paper / pulp is generally used for processed cellophane, regenerated cellulose fiber, and the like.

  Until now, in order to give mechanical strength to cellulosic resin moldings, or to give a good cellular state and uniform mechanical properties as a foam, to modify cellulose (Patent Document 1), It has been proposed to crosslink a biodegradable resin (Patent Document 2).

  These require unique materials and man-hours to modify or crosslink cellulose, and are not limited to obtaining biodegradable cellulose compositions and molded articles thereof, and foams thereof. In light of the objective of further contributing to resource conservation and environmental protection by manufacturing cheaply with fewer man-hours, it was not yet satisfactory.

  By the way, so-called sugar beet (sugar radish) is consumed in the country next to sugar cane as a raw material of sugar that represents sweeteners. Sugar made from sugar beet is also called beet sugar, and a large amount of squeezed rice cake (residue) is generated during the sugar production process. Beet pulp, which is a squeezed koji, is used as a raw material for feed for ruminants such as cows as raw pulp or dried pulp.

  In addition, the component of dietary fiber in sugar beet produced from this residue is also called beet fiber (Sugar beet fiber), which is a natural functional food material. Some are supplied as

Sugar beet is a kind of root vegetable, but among those belonging to this root vegetable, in addition to sugar beet, for example, there are potatoes, but this potato is consumed in large quantities for the purpose of collecting potato starch other than edible, There is no industrially or industrially effective use of starch cake (potato pulp) generated in the process of producing starch, and some of it is still used as feed for cattle, etc. It is only composted.
JP 2003-119310 A JP 2004-352750 A

  The present invention has been made paying attention to the circumstances as described above. The purpose of the present invention is to use the root vegetables squeezed as a cellulosic resource, and to produce feed materials and functional food materials for ruminants such as cattle. The object of the present invention is to provide a cellulose-containing biodegradable resin composition and its foam that can be widely used in the fields of industry and other industries, beyond the conventional range of use.

  In order to solve the above-mentioned problems, the cellulose-containing biodegradable resin composition and the foamed product thereof according to the present invention are characterized by using a root vegetable pomace as a cellulose resource of the cellulose-containing biodegradable resin composition. Although it is possible to use cellulose derived from paper / pulp as a cellulose resource because of its availability, it cannot be used to solve the above problem due to its poor dispersibility. Details will be described later.

  The present invention is characterized in that it is a cellulose-containing biodegradable resin composition containing a root squeezed rice cake, a biodegradable thermoplastic resin, a foaming agent, and a foaming aid. Here, the root vegetables used to solve the above-mentioned problems are those in which cocoons are generated in the root vegetables except for edible use, and typical examples include sugar beets and potatoes.

  Moreover, when utilizing the root vegetables squeezed as a cellulose resource, a plurality of types of root vegetables such as a mixture of sugar beet and potato squeezed potatoes may be used in combination.

  As the biodegradable thermoplastic resin used together with the root vegetables of the present invention as a cellulose resource, any known biodegradable resin can be used.

  The cellulose-containing biodegradable resin composition of the present invention contains a foaming agent and a foaming aid, and the foaming aid is preferably a natural resin, a hydrocarbon resin, or a modified resin thereof.

  It is preferable that 1-40 mass parts of the said foaming adjuvant is included with respect to a total of 100 mass parts of solid content of the root squeezed rice cake, and a biodegradable thermoplastic resin.

  The cellulose-containing biodegradable resin composition of the present invention may further contain a dispersant. In general, cellulose has strong hydrophilicity due to the hydroxyl group it has, but the dispersant of the present invention enhances the mutual dispersibility between the root vegetables squeezed and the biodegradable thermoplastic resin, It can be mixed uniformly.

  In the present invention, alkenyl succinic anhydride or alkyl ketene dimer is particularly preferably used as the dispersant.

  The cellulose-containing biodegradable resin foam of the present invention is obtained by foaming the resin composition.

  The foam comprising the cellulose-containing biodegradable resin composition of the present invention exhibits sufficient biodegradability. In addition, since this composition uses root vegetables squeezed as a cellulose resource, it is superior in terms of resource problems and environmental problems compared to conventional foams such as polystyrene foam and polyurethane foam. Applications in a wide range of fields can be expected instead of these foams.

  Although the cellulose-containing biodegradable resin foam of the present invention depends on the season and soil conditions, or the conditions such as the shape and thickness of the foam, it can be buried in the soil for a period of about 15 to 50 days. It biodegrades to the extent that it does not retain its original shape and returns to the soil.

  The cellulose-containing biodegradable resin composition according to the present embodiment can be obtained by uniformly mixing a root vegetable pomace as a cellulose resource, a biodegradable thermoplastic resin, a foaming agent, and a foaming aid.

  Root vegetables are those that use the portion of the vegetable that exists in the soil. In addition to the above-mentioned sugar beet and potatoes, there are sweet potatoes, radishes, onions, carrots, raccoon, burdock, garlic and the like.

  This root vegetable squeezed koji refers to what remains after taking out these useful ingredients such as sugar and starch in the process of producing sugar and starch using root vegetables as a raw material.

  Depending on the type of root vegetable that is the source of the root vegetables, the form at the time of acquisition, and the degree of processing, the root vegetables must be dried, moist, or scratched or coarse. Various forms can be used.

  Furthermore, in this embodiment, the squeezed koji of root vegetables is used as a cellulose resource, but when using the koji koji itself, it is of course possible to add processing to the koji kneaded and adjust the ingredients. Even if it is a thing etc., if it contains the cellulose component originally contained in the pomace and uses the cellulose contained in it, it is included in the meaning which utilizes the pomace of root vegetables as a cellulose resource. .

  The biodegradable thermoplastic resin is generally described as a biodegradable resin in the state of use, which exhibits the same function as a conventional synthetic resin, and when discarded after use, in soil or seawater. It is decomposed by the action of medium microorganisms and enzymes, etc. until the original shape at the time of disposal is retained, and finally has the property of becoming water and carbon dioxide, and the calories generated when burned are as low as paper Therefore, no harmful substances such as dioxins are generated.

  Examples of biodegradable resins include cellulose acetate, polybutylene succinate, polycaprolactone, polyvinyl alcohol, caprolactone-butylene succinate, polybutylene adipate terephthalate, adipate modified polybutylene succinate, carbonate modified polybutylene succinate, polyethylene There are synthetic resin types such as terephthalate succinate, polyethylene succinate and polyhydroxybutyrate, and natural material types such as starch, cellulose, cellulose acetate and polylactic acid.

  The biodegradable thermoplastic resin in the present embodiment is a material that can exhibit the features of the present invention without departing from the gist of the present invention, even if it is a material to be discovered or developed in the future. The type is not particularly limited.

  The blending ratio of the root vegetables squeezed as a cellulose resource and the biodegradable thermoplastic resin is arbitrarily determined according to the characteristics of the biodegradable thermoplastic resin to be used in order to express the characteristics required as a foam. Generally, however, if the ratio of cellulose is high, the foam is hard and brittle, and if the ratio of biodegradable thermoplastic resin is high, the foam is flexible and excellent in moldability. Considering these points, the preferred blending ratio of the root vegetables squeezed as a cellulose resource and the biodegradable thermoplastic resin is 1:99 to 90:10, more preferably 20:80 to the mass ratio of the former: the latter. 80:20. If the mixing ratio of the root vegetable pomace as a cellulose resource is too small, the merit of effectively using the root pomace as a cellulose resource as a material for the biodegradable resin composition and the foam cannot be fully utilized. On the other hand, if the blending ratio of the root vegetables squeezed as a cellulose resource is too large, even if an appropriate amount of a dispersant or a foaming aid is added, the fluidity of the composition before foaming decreases, It becomes difficult to obtain a foam, and even if a foam is obtained, it is difficult to obtain a foam-molded product of stable quality (physical properties and appearance).

  The cellulose-containing biodegradable resin composition of this embodiment contains a foaming agent as an essential component other than the above. The foaming agent that can be used in the present invention may be of a type that decomposes by heat to release a gas, or may vaporize by heat to expand in volume to form bubbles, but is preferably 80 to 250 ° C. Preferably, gas is generated or vaporized at 100 to 180 ° C.

  As the former type of foaming agent that can be decomposed, those used for forming ordinary plastic foams can be used. Examples of this type include azo foaming agents, hydrazine foaming agents, semicarbazide foaming agents, triazole foaming agents, N-nitroso foaming agents, sodium bicarbonate and the like.

  In addition, examples of the latter type of foaming agent that can be vaporized include water, methanol, ethanol, and the like, or a mixture thereof. Water is a particularly preferable foaming agent in the present invention. Because, when using as a raw material cellulose beaten from sugar beet of sugar beet, water as a foaming agent is contained in the fibrous cellulose, so only for the purpose of functioning as a foaming agent later It is because it is not necessary to add.

  In the case of using any of these foaming agents, 0.01 to 30 parts by mass, preferably 100 parts by mass with respect to a total of 100 parts by mass of the solid content of the root vegetables and the biodegradable thermoplastic resin. 0.1-20 mass parts is contained. Although it is not exactly known, the water that contributes as a foaming agent when using the above fibrous cellulose is determined based on the solid content of the cellulose material used and the amount of other components, etc. It is thought that it will be about 10-20 mass parts with respect to 100 mass parts per minute.

  The expansion ratio when foaming the cellulose-containing biodegradable resin composition of the present embodiment is preferably in the range of 10 to 100 times. When the expansion ratio is less than 10 times, the cushioning properties, lightness, and flexibility required for the foam are reduced. On the other hand, when the expansion ratio exceeds 100 times, mechanical properties and molding processability required for the foam are deteriorated.

  In the cellulose-containing biodegradable resin composition of the present invention containing a foaming agent, the expansion ratio tends to increase as the content ratio of the biodegradable thermoplastic resin increases as compared with the content ratio of the cellulose component. is there.

The expansion ratio as used in the present embodiment refers to a value calculated according to the following equation by measuring the apparent density defined in JIS-K-6767.
Foaming ratio = apparent density of foam before molding / apparent density of foam

  In the present embodiment, the foaming assistant is a zinc compound such as zinc oxide or zinc stearate, an organic acid such as salicylic acid, phthalic acid or oxalic acid, or a urethane foaming assistant such as dichloromethane or polystyrene. Unlike a general foaming aid such as a certain chloroethane, it means an additive having an action of adjusting the fluidity of the biodegradable resin composition at the time of foaming and promoting foaming, and the biodegradability of the present invention This is an essential component for foaming the resin composition within a suitable range.

  In this case, the fluidity means that a thermoplastic foam is formed in a stage before the biodegradable resin composition or foam is formed in order to form a preferable foamed state when the biodegradable resin composition of the present embodiment is foamed. It is a specific property that a biodegradable resin molding must have. The good fluidity means that the foamability of the biodegradable resin composition of the present embodiment is good and the stability in the foamed state is good.

  The cellulose-containing biodegradable resin composition of the present invention adjusts the flowability of root vegetables as a cellulose resource, biodegradable thermoplastic resin, foaming agent, and biodegradable resin composition during foaming. It can be obtained by using the foaming auxiliary agent, which is an additive, as an essential component and mixing other compounding agents as necessary.

  In this embodiment, sugar beet squeezed rice cake is a process of producing sugar from sugar beet juice, also called sugar radish, that is, a squeezed rice cake that is a residue generated in the sugar beet sugar production process, Is starch potato (potato pulp) generated in the process of producing potato starch as described above.

  Describing the use of sugar beet squeezed as a squeezed root vegetable that is a cellulosic resource, by mixing the sugar beet squeeze produced in the sugar beet sugar production process with water while heating in a pressurized state, You can use what you beat. Since the color is slightly brownish, the so-called bleaching or decoloring treatment may be performed as necessary when the color affects the application or quality.

  As another preferred form of squeezed sugar beet as a cellulose resource, beet fiber (Sugar beet fiber) supplied as the above-mentioned natural functional food material can be used. This beet fiber has a high fiber content such as 23% by mass of cellulose and 36% by mass of hemicellulose, but the same is true for the squeezed koji itself, which is a residue generated in the beet sugar manufacturing process. It is considered that the fiber content is.

  By doing so, it is possible to more effectively utilize the sugar beet of sugar beet that has been produced in large quantities in the beet sugar manufacturing process, which has not been used effectively so far.

  On the other hand, when potato squeezed potato is used as the squeezed potato for root vegetables which are cellulose resources, the starch potato (potato pulp) generated in the potato starch production process has a water content of about 75% by mass. It contains a lot of cellulose and starch and has a wet short fiber-like appearance. This can be dried and used in the form of powder or sand. However, since it is slightly brownish, the so-called bleaching or decoloring treatment may be performed as necessary if the color affects the use and quality.

  By doing so, it is possible to more effectively utilize the potato squeezed potatoes that have been produced in large quantities in the starch production process, which has not been used effectively so far.

  Moreover, when utilizing the root vegetable squeezed rice cake as a cellulose resource, a side dish and a potato squeezed rice cake may be mixed and used. This is because it can be expected that squeezed meals of both side dishes and potatoes, which are residues generated in large quantities of root vegetables that have not been used effectively so far, can be used more effectively.

  As a result of intensive studies by the present inventors, the cellulose-containing biodegradable resin composition of the present embodiment foams well, and in order to stably exhibit foamability, in addition to blending the foaming agent in an appropriate amount, It has been found that the fluidity in the state of the composition before foaming or in the state of the molded product before foaming should be appropriately adjusted, and for that purpose, an appropriate amount of a specific foaming aid should be blended.

  Examples of such specific foaming aids preferably used in the present embodiment include natural resins, hydrocarbon resins or modified products thereof, and these may be blended alone or in combination of two or more. Any combination can be used. Examples of natural resins include rosin, copal, dammar, shellac, etc .; modified products thereof include rosin esters and polymerized rosin esters that are modified products of polyhydric alcohols (such as glycerin and pentaerythritol) of rosin and polymerized rosin. Such rosin ester resins, hydrogenated rosins and the like can be mentioned. Examples of hydrocarbon resins and modified products thereof (hydrogenated products, etc.) include “Quinton (registered trademark)” (manufactured by Nippon Zeon Co., Ltd.), “Escollets” (manufactured by Exxon Mobil Corp.), “Arcon (registered trademark)” (Made by Arakawa Chemical Industry Co., Ltd.) and terpene resins and modified products thereof such as “Clearon (registered trademark)” (made by Yasuhara Chemical Co., Ltd.).

  These foaming assistants can be added in an amount of preferably 1 to 40 parts by weight, more preferably 1 to 30 parts by weight, based on a total of 100 parts by weight of the solid content of the root vegetables and the biodegradable thermoplastic resin. . If the blending amount of the foaming aid is insufficient, foaming tends to be poor. Conversely, if the blending amount of the foaming aid is too large, the foamed molded product tends to have insufficient strength.

  In the present embodiment, a dispersant can be further added for the purpose of improving the uniform mixing property when preparing the composition and improving the uniform foaming property and further the water resistance of the resin foam. In particular, when fibrous cellulose is used as a squeezed root vegetable as a cellulose resource, the fibrous cellulose is in a so-called swollen state at the time of blending, so that it is miscible with the biodegradable thermoplastic resin blended together. Since it may be insufficient, it is necessary to add a dispersant. This dispersant may be added in an amount of preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the solid content of the squeezed koji and the biodegradable thermoplastic resin. .

  As the dispersant used in the present invention, alkenyl succinic anhydride and / or alkyl ketene dimer is particularly preferably used, and either one or both of them can be used in combination.

  Here, as alkenyl succinic anhydride, what is generally marketed as a paper sizing agent can also be used. Similarly, as an alkyl ketene dimer, what is generally marketed as a paper sizing agent can also be used.

  The blending amount of the alkenyl succinic anhydride and / or the alkyl ketene dimer is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the root vegetables as the cellulose resource. is there. Even if blended in a larger amount than 30 parts by mass, dispersibility and water resistance with a higher biodegradable resin can no longer be obtained, and this is an obstacle to biodegradability of cellulose. On the other hand, when the blending amount is less than 0.1 parts by mass, no improvement in uniform mixing property is observed.

  Further, as a resin component other than the biodegradable thermoplastic resin, a thermoplastic resin such as polyethylene, polypropylene, ethylene-propylene random copolymer, polyvinyl acetate, or polybutene may be blended. Since it cannot deny that the decomposability is hindered, it is better to keep it to a small extent.

  The biodegradable resin composition according to the present invention may further contain other additives as long as the effects of the present invention are not impaired. For example, lubricant, pigment, bleach, pigment, dye, flame retardant, flame retardant aid, antistatic agent, plasticizer, antibacterial agent, biodegradation accelerator, foaming agent decomposition accelerator, antiblocking agent, UV absorber, Antioxidants, fillers, deodorants, thickeners, foaming aids, cell stabilizers, etc. may be used alone or in combination of two or more.

  The cellulose-containing biodegradable resin composition of the present invention can be obtained, for example, by mixing using a high-speed mill, a Henschel mixer, or a kneader, which is a normal powder mixer. When blending a liquid foaming agent, the foaming agent may be mixed with the homogeneous mixture, or mixed with the foaming agent when some of the components are mixed, and then the remaining components are mixed. Also good.

  Foam molding is performed by extruding a uniform raw material mixture containing a foaming agent from an extruder, heating it under pressure to open it rapidly, or in the case of a vaporizable foaming agent, heating it at a temperature equal to or higher than the boiling point of the foaming agent. . At this time, an air-conditioning agent widely used for foam molding such as polystyrene can also be used. The heating temperature in foam molding may be appropriately selected according to the type of foaming agent, the blending ratio of cellulose, the type of biodegradable thermoplastic resin, the blending amount of each material, etc., but preferably 80 to 250 ° C. More preferably, it is 100-180 degreeC. When the foaming agent is water, the foam is formed by evaporating water by heating in this foaming step.

  The cellulose-containing biodegradable resin foam of the present invention can be used for various applications. For example, bottles, films or sheets, hollow tubes, laminates, molded containers, filaments, non-woven fabrics, shopping bags, paper bags, shrink films, garbage bags, compost bags, lunch boxes, prepared food containers, food / confectionery packaging films, Diapers, sanitary napkins, various wrap films, agricultural and horticultural films, greenhouse films, fertilizer bags, packaging bands, films for magnetic tape cassette products such as video and audio, flexible disk (FD) packaging films, Film for plate making, adhesive tape, tape, yarn, seedling pot, waterproof sheet, sandbag bag, architectural film, weed prevention sheet, vegetation net, various packaging films for food, electronics, medical, medicine, cosmetics, agriculture -Suitable for use in a wide range of materials, such as materials used in the civil engineering and fisheries fields It may be.

  In the present invention, a particularly suitable shape of the biodegradable foam may be a sheet. By using a sheet shape, not only the productivity is good, but also the period required for biodegradation can be expected to be shorter than other shapes. When the biodegradable resin foam of the present invention is used as a sheet, the thickness of the biodegradable resin foam sheet is preferably in the range of 0.1 to 5 mm. When the thickness of the foam sheet is less than 0.1 mm, the cushioning characteristic as the foam is lowered, and when it is thicker than 5 mm, the rigidity of the foam sheet becomes too high, and as a result, the flexibility of the foam sheet is lowered. When the foam is used in a form other than the sheet, it is appropriately determined depending on the relationship between the thickness and size required for the form, the buffering property, the flexibility, and other physical properties.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the cellulose-containing biodegradable resin foam of the present invention can be used in various forms without being limited to a sheet-like material, They are all included in the technical scope of the present invention.

Example 1
1 kg of sugar beet squeezed from the sugar beet production process (mixed with a strip or chopped sugar beet) and 5 kg of water are mixed in an autoclave at 130 ° C. for 1 hour ( By heating in a pressurized state (due to the vapor pressure contribution), the squeezed rice cakes that were strip-shaped or scratched were beaten into fibers.

  The obtained fibrous cellulose was blended with 30 g of alkenyl succinic anhydride (manufactured by Arakawa Chemical Industries; trade name “Sizepine (registered trademark) SA-862”) promptly while maintaining the temperature, and well blended. Squeezed. 400 g (15% solid content) of this beaten product is taken, and 30 g of polybutylene succinate (manufactured by Showa Polymer; trade name “Bionore (registered trademark) # 1001”) as a biodegradable thermoplastic resin and rosin 10 g of ester (manufactured by Arakawa Chemical Industries; trade name “Ester Gum AAL”) was added and heated and mixed at 110 ° C. with a lab plast mill. This composition was molded into a sheet having a thickness of 0.2 mm by hot pressing at 110 ° C. When this was further placed in a 30 cm × 30 cm × 3 mm mold and heated to 180 ° C., the sheet foamed to form a foam full of the mold. The obtained sheet-like foam exhibited a uniform cell state and the expansion ratio was 14 times. When this foam was buried in organic soil at about 25 ° C. and biodegradability was evaluated, biodegradation progressed in one month and the original shape was not retained.

Example 2
The same composition except that polybutylene succinate used as a biodegradable thermoplastic resin in Example 1 was changed to 30 g of polycaprolactone (manufactured by Daicel Chemical Industries; trade name “CELGREEN (registered trademark) PH7”). The mixture was heated and mixed at 100 ° C. with a plastmill. This composition was molded into a sheet having a thickness of 0.2 mm by hot pressing at 110 ° C. When this was further placed in a 30 cm × 30 cm × 3 mm mold and heated to 180 ° C., the sheet foamed to form a foam full of the mold. The obtained sheet-like foam exhibited a uniform cell state and the expansion ratio was 15 times. When this foam was buried in organic soil at about 25 ° C. and biodegradability was evaluated, biodegradation progressed in one month and the original shape was not retained.

Example 3
The rosin ester used as the foaming aid in Example 1 has the same composition except that it is changed to 10 g of a modified hydrocarbon resin (manufactured by Arakawa Chemical Industries; trade name “Arcon (registered trademark) P100”). Heat mixing was performed at 110 ° C. This composition was molded into a sheet having a thickness of 0.2 mm by hot pressing at 120 ° C. When this was further placed in a 30 cm × 30 cm × 3 mm mold and heated to 180 ° C., the sheet foamed to form a foam full of the mold. The obtained sheet-like foam exhibited a uniform cell state and the expansion ratio was 14 times. When this foam was buried in organic soil at about 25 ° C. and biodegradability was evaluated, biodegradation progressed in one month and the original shape was not retained.

Example 4
As squeezed sugar beet as a cellulose resource, beet fiber (manufactured by sugar beet sugar; powder type) 60 g, polybutylene succinate (made by Showa Polymer; trade name “Bionore (registered trademark) # 1001”) 30 g, alkenyl 3 g of succinic anhydride (Arakawa Chemical Industries; trade name “Sizepine (registered trademark) SA-862”), 10 g of rosin ester (Arakawa Chemical Industries; trade name “Estimum AAL”), 5 g of sodium bicarbonate The mixture was heated and mixed at 110 ° C. using a lab plast mill. This composition was molded into a sheet having a thickness of 0.2 mm by hot pressing at 110 ° C. When this was further placed in a 30 cm × 30 cm × 3 mm mold and heated to 180 ° C., the sheet foamed to form a foam full of the mold. The obtained sheet-like foam had uniform bubbles, and the expansion ratio was 15 times. When this foam was embedded in organic soil at about 25 ° C. and biodegradability was evaluated, decomposition progressed in one month and the original shape was not retained.

Example 5
30 g of beet fiber (manufactured by Japanese sugar beet sugar; powder type) and 30 g of polybutylene succinate copolymer (manufactured by Daicel Chemical Industries; trade name “CELGREEN (registered trademark) SBC101”) as squeezed sugar beet as a cellulose resource Alkenyl succinic anhydride (manufactured by Arakawa Chemical Industries; trade name “Sizepine (registered trademark) SA-862”) 3 g, modified hydrocarbon resin (manufactured by Arakawa Chemical Industries; trade name “Arcon (registered trademark) P100”) 10 g and 5 g of sodium bicarbonate were blended and heated and mixed at 110 ° C. with a lab plast mill.

  When this composition was placed in a 30 cm × 30 cm × 3 mm mold as it was without being molded by hot press and heated to 180 ° C., the sheet foamed to form a foam full of the mold. The obtained sheet-like foam exhibited a uniform cell state and the expansion ratio was 15 times. When this foam was embedded in organic soil at about 25 ° C. and biodegradability was evaluated, decomposition progressed in one month and the original shape was not retained.

Example 6
60 g of potato pulp obtained by collecting potato starch from potatoes and dried with hot air, 30 g of polybutylene succinate (made by Showa Polymer; trade name “Bionore (registered trademark) # 1903”), alkenyl anhydride 3 g of acid (made by Arakawa Chemical Industries; trade name “Sizepine (registered trademark) SA-862”), 10 g of rosin ester (made by Arakawa Chemical Industries; trade name “Superester A100”), and 10 g of sodium bicarbonate were added to the laboratory. The sheet was molded into a sheet having a thickness of 0.5 mm by a hot press at 110 ° C. using a plast mill. When this was further placed in a 30 cm × 30 cm × 3 mm mold and heated to 160 ° C., the sheet foamed to form a foam full of the mold. The obtained sheet-like foam had uniform bubbles, and the expansion ratio was 15 times. When this foam was embedded in organic soil at about 25 ° C. and biodegradability was evaluated, decomposition progressed in one month and the original shape was not retained.

Example 7
30 g of polybutylene succinate copolymer (manufactured by Daicel Chemical Industries, Ltd .; trade name “CELGREEN (registered trademark) SBC101”), 60 g of alkenyl after potato starch is collected from potatoes and dried with hot air 3 g of succinic anhydride (Arakawa Chemical Industries; trade name “Sizepine (registered trademark) SA-862”), 10 g of rosin ester (Arakawa Chemical Industries; trade name “Superester A100”) and 15 g of sodium bicarbonate Then, the mixture was heated to 110 ° C. with a lab plast mill. When the composition thus obtained was placed in a 30 cm × 30 cm × 3 mm mold and heated to 170 ° C., the composition foamed to form a foam full of the mold. The obtained sheet-like foam had uniform bubbles, and the expansion ratio was 15 times. When this foam was embedded in organic soil at about 25 ° C. and biodegradability was evaluated, decomposition progressed in one month and the original shape was not retained.

Comparative Example 1
The sugar beet squeezed used in Example 1 was replaced with 1 kg of softwood pulp (product of CMPC; trade name “NBKP”), and this and 5 kg of water were put into a kneader and beaten in a fibrous form. 30 g of alkenyl succinic anhydride (manufactured by Arakawa Chemical Industries; trade name “Sizepine (registered trademark) SA-862”) was blended in the slurry thus obtained, and the mixture was squeezed well. 60 g of this dried in a hot air dryer was taken, and 30 g of polybutylene succinate (made by Showa High Polymer; trade name “Bionore (registered trademark) # 1903”) as a biodegradable thermoplastic resin, rosin 10 g of ester (made by Arakawa Chemical Industries; trade name “Superester A100”) was added and mixing was attempted with heating at 120 ° C. using a lab plast mill. Therefore, the heating and mixing were stopped. As a result, a uniform mixed composition could not be obtained.

Comparative Example 2
Take 30 g of softwood pulp (CMPC; trade name “NBKP”) obtained in the same manner as in Comparative Example 1 and beaten into a fiber and dried with a hot air dryer. As a thermoplastic resin, 30 g of polybutylene succinate (made by Showa Polymer; trade name “Bionore (registered trademark) # 1903”) and 10 g of rosin ester (made by Arakawa Chemical Industries; trade name “Super Ester A100”) are added. The mixture was heated and mixed at 120 ° C. in a lab plast mill. This composition was molded into a 1 mm thick sheet by hot pressing at 110 ° C. However, the dispersion of the pulp components was poor and a homogeneous sheet could not be obtained. (See FIG. 1).

Comparative Example 3
By mixing 1 kg of the same side dish squeezed rice cake as in Example 1 and 5 kg of water and heating it in a pressurized state at 130 ° C. for 1 hour (contributing to vapor pressure), a strip shape or a scratched shape. The squeezed rice cake was beaten into a fiber shape. The obtained fibrous cellulose was quickly blended with 30 g of alkenyl succinic anhydride (manufactured by Arakawa Chemical Industries; trade name “Sizepine (registered trademark) SA-862”) while maintaining the temperature, and then squeezed well. It was. 400 g (15% solid content) was taken from this beaten product, and 30 g of polybutylene succinate (made by Showa High Polymer; trade name “Bionore (registered trademark) # 1001”) as a biodegradable thermoplastic resin was added thereto. The rosin ester which is the foaming aid of Example 1 was not blended, and was heated and mixed at 110 ° C. with a lab plast mill. This composition was molded into a sheet having a thickness of 0.2 mm by hot pressing at 110 ° C. Even when this was further placed in a 30 cm × 30 cm × 3 mm mold and heated to 180 ° C., the sheet hardly foamed and the thickness of the sheet hardly changed.

Comparative Example 4
To 60 g of the same cellulose (beat fiber) as in Example 5, 30 g of polybutylene succinate copolymer (manufactured by Daicel Chemical Industries; trade name “CELGREEN (registered trademark) SBC101”), alkenyl succinic anhydride (manufactured by Arakawa Chemical Industries; 3 g of trade name “Sizepine (registered trademark) SA-862”) and 5 g of sodium bicarbonate were added, and the mixture was heated and mixed at 110 ° C. with a lab plast mill without blending the hydrocarbon resin as the foaming aid of Example 5. This composition was molded into a sheet having a thickness of 0.2 mm by hot pressing at 110 ° C. Even if this is further placed in a 30 cm × 30 cm × 3 mm formwork and heated to 180 ° C., the sheet hardly foams, and when the surface of the sheet is enlarged and observed with a microscope, fine irregularities that appear to be caused by foaming are observed on the surface. Was only observable.

6 is a photograph showing a dispersed state of softwood pulp in a sheet-like molded product of Comparative Example 2.

Claims (5)

Contains root squeezed rice cake, biodegradable thermoplastic resin, foaming agent and foaming aid ,
The foaming aid is a natural resin, a hydrocarbon resin, or a modified resin thereof,
Cellulose-containing biodegradable resin composition the amount of blowing aid to a total of 100 parts by mass of the solids and biodegradable thermoplastic resin root vegetable pomace is characterized 1 to 40 parts by der Rukoto.   The cellulose-containing biodegradable resin composition according to claim 1, wherein the squeezed koji of the root vegetables is a sugar beet and / or potato pomace. The cellulose-containing biodegradable resin composition according to claim 1 or 2 , further comprising a dispersant as another component. The cellulose-containing biodegradable resin composition according to claim 3 , wherein the dispersant is an alkenyl succinic anhydride and / or an alkyl ketene dimer. A cellulose-containing biodegradable resin foam obtained by foaming the resin composition according to any one of claims 1 to 4 .